US9780354B2 - Battery electrode material and method for making the same - Google Patents

Battery electrode material and method for making the same Download PDF

Info

Publication number
US9780354B2
US9780354B2 US13/996,781 US201113996781A US9780354B2 US 9780354 B2 US9780354 B2 US 9780354B2 US 201113996781 A US201113996781 A US 201113996781A US 9780354 B2 US9780354 B2 US 9780354B2
Authority
US
United States
Prior art keywords
conductive particles
polymer
solvent
electric field
lines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US13/996,781
Other versions
US20130316245A1 (en
Inventor
Mark Buchanan
Geir HELGESEN
Matti KNAAPILA
Preben J.S. Vie
Gorm Krogh Johnsen
Rahul Fotedar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Condalign AS
Original Assignee
Condalign AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Condalign AS filed Critical Condalign AS
Assigned to CONDALIGN AS reassignment CONDALIGN AS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KROGH JOHNSEN, Gorm, FOTEDAR, RAHUL, VIE, PREBEN J.S., BUCHANAN, MARK, HELGESEN, GEIR, KNAAPILA, MATTI
Publication of US20130316245A1 publication Critical patent/US20130316245A1/en
Application granted granted Critical
Publication of US9780354B2 publication Critical patent/US9780354B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to electrode materials. More specifically, the invention relates to battery electrode materials and to a method for forming such battery electrode materials.
  • Electrochemical devices for energy storage and energy conversion such as batteries and fuel cells contain electrodes and electrolytes to transport and harvest charges. These elements are electrically conductive, ionically conductive or both. These processes may be limited either by the electrode and membrane material's inherent conductivity level or a non-optimal electrode configuration or both.
  • Rechargeable batteries (or electrochemical cells) contain two electrodes which are connected through an electrolyte. These components may be prepared from a variety of materials but in general the electrode-electrolyte interface often limits efficiency of charge transport. If this interface was larger and if the distance between the electrodes was smaller, the charge transport would be more efficient.
  • a better electrode design would therefore be influential in improving the battery function.
  • U.S. Pat. No. 7,828,619 discloses a method for preparing a nanostructured composite electrode through electrophoretic deposition, and electrodes prepared by such a method.
  • a material comprising nanoparticles and carbon nanotubes having a high aspect ratio is directly deposited on the electrode and contains no polymer.
  • Electrodes are produced in which conductive particles are aligned in an ionomer polymer upon application of an electric field. None is mentioned about batteries.
  • WO 2010/151141 discloses a method for manufacturing an electrostatic discharge device comprising a layer of conductive particles in a cross linked polymer matrix. The method involves curing of the polymer.
  • a battery In contrast to a fuel cell, which will function as long as fuel and oxygen are supplied to it, a battery will be discharged upon use. Cost and environmental concerns make rechargeable batteries attractive. Other important aspects of batteries are weight and performance after a number of charge/discharge cycles. Batteries having a low weight and/or retaining a high percentage of their initial charge after a large number of charge/discharge cycles are desirable. Common battery electrodes contain carbon and binder in order to improve conductivity. However, the carbon and binder together often constitute approximately 50% of the battery electrode material thereby contributing to the weight of the electrode and eventually the battery. It would be desirable to decrease the battery electrode weight while maintaining and/or improving the battery performance.
  • a method for manufacturing of a battery electrode material comprising the steps of:
  • the present invention is based on the insight that subjecting a mixture comprising at least one polymer and randomly distributed conductive particles to an electric field results in alignment of the conductive particles.
  • align and alignment are intended to mean that the conductive particles form lines that are oriented in the same or substantially the same direction as the electric field line. It is to be understood that in the context of the lines the term “oriented in the same direction as the electric field line” means that the lines are co-linear or parallel to the electric field line or deviate from the electric field line with an angle of 45° or less. For instance, the direction may be in-plane or out-of-plane as described below.
  • the lines of particles may be co-linear or parallel to each other.
  • the alignment of conductive particles into lines results in conductive pathways in the polymer.
  • the conductivity will be high in the direction of the lines of conductive particles and low or non-existing in the direction perpendicular to said lines of conductive particles; i.e. the formed battery electrode material will be anisotropic with respect to the direction of conductivity.
  • the pathways are able to enhance the macroscopic conductivity of the material.
  • the formation of conductive pathways allows the battery electrode material to become conductive also when it contains a lower amount of conductive particles than is otherwise necessary for creating an electrical contact for the material when it contains randomly distributed conductive particles.
  • the amount of conductive particles may thereby be reduced and may be at least ten times lower than the percolation threshold.
  • Concentrations of conductive particles may be in the range of 0.2-10 vol %, 0.2-2 vol %, or 0.2-1.5 vol %.
  • the percolation threshold is defined as the lowest concentration of conductive particles in the polymer necessary to achieve long range conductivity in a system where the conductive particles are randomly distributed.
  • long range conductivity refers to the conductivity of the composite comprising conductive particles and at least one polymer.
  • a straight line of particles is defined as a line of particles lacking lines of particles branching out from it.
  • the electric field may be created between electrodes that can be placed either in direct contact with one or both sides of the least one polymer, conductive particles and at least one solvent or outside additional insulating layers.
  • the electrodes may be removed after formation of the battery electrode material.
  • the direction of the electric field may be determined by the electrode arrangement leading to a specific orientation of the lines of conductive particles.
  • the lines of conductive particles may extend between the electrodes in an in-plane or out-of-plane direction.
  • the lines of conductive particles extend in a co-linear or substantially parallel fashion with the electrodes they are said to be aligned in an in-plane alignment.
  • the lines of conductive particles extend in a perpendicular or substantially perpendicular fashion with the electrodes they are said to be aligned in an out-of-plane alignment.
  • the method as defined hereinbefore or hereinafter further comprises a step comprising supporting said at least one polymer, conductive particles and at least one solvent on a support.
  • the support may be a glass table, an electrode, a conductive metal foil or an electrode comprising a conductive metal foil.
  • the conductive metal foil may comprise aluminium or copper.
  • the supporting of the said at least one polymer, conductive particles and at least one solvent on a support includes spreading in order to obtain a layer.
  • the layer may be uniform or non-uniform.
  • the maximum thickness of the layer may be between 5 ⁇ m (micrometer) and 2 cm (centimeter). In a further embodiment the maximum thickness of the layer may be between 5 ⁇ m and 2 mm (millimetre). In still a further embodiment the maximum thickness of the layer may be between 10 ⁇ m and 2 mm.
  • steps a) and b) in the method as defined hereinbefore or hereinafter may at least partly overlap. No or little alignment of the lines of particles will take place if the electric field is in step b) is turned off too early. Step b) may be continued after turning off the electric field in step b) in order to further dry the electrode material after alignment of the lines of conductive particles.
  • the time for drying in step b) will depend on factors such as temperature, pressure, thickness of the layer and the solvent being used. Typically, a layer having a thickness of approximately 50 ⁇ m is dried for five minutes between 50 to 100° C., such as 80° C., under atmospheric pressure when the solvent is N-methyl-2-pyrrolidine.
  • the at least one polymer in the mixture may be a conductive or non-conductive polymer.
  • the conductive polymer may be an ionomer such as Nafion®.
  • the at least one polymer may be a single kind of polymer or a mixture of different polymers. Suitable polymers include, but are not limited to, polyvinyldifluoride (PVDF), carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), poly(3,4-ethylenedioxythiophene) (PEDOT), polyacrylic acid (PAA) and alginate.
  • PVDF polyvinyldifluoride
  • CMC carboxymethylcellulose
  • SBR styrene butadiene rubber
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PAA polyacrylic acid
  • alginate alginate.
  • the at least one polymer may be curable or non-curable. It will be appreciated that when the at least one polymer is
  • step a) is a non-curable polymer
  • the conductive particles are infusible particles such as carbon particles or metal particles.
  • conductive carbon particles include, but are not limited to, carbon-black, nanocones, carbon nanotubes, graphene particles or disk-like carbon particles.
  • conductive metal particles include, but are not limited to, silver or iron and oxides thereof.
  • the metallic conductive metal particles may be metallic powders. Further, the conductive particles may be electronically or ionically conductive. The conductive particles may be the same or different.
  • the conductive particles have a low aspect ratio.
  • the invention is not limited to conductive particles having a low aspect ratio.
  • the aspect ratio is defined as the ratio between the largest linear dimension of a particle such as a conductive particle and the largest dimension perpendicular to said largest dimension.
  • Low aspect ratio refers to an aspect ratio that is equal to or less than 20:1.
  • low aspect ratio refers to an aspect ratio that is equal to or less than 10:1.
  • low aspect ratio refers to an aspect ratio that is equal to or less than 5:1.
  • the at least one solvent in step a) in the method as defined hereinbefore or hereinafter is water or an organic solvent such as hexane or mixtures thereof.
  • the organic solvent may be miscible or immiscible with water. Further, the organic solvent may be protic or non-protic.
  • the at least one solvent is N-methyl-2-pyrrolidone (NMP).
  • step a) further comprises active particles.
  • the active particles may be the same or different.
  • active particles is meant particles giving the battery its ability to store lithium ions.
  • the active particles may align together with the conductive particles.
  • active particles include, but are not limited to platinum, lithium-metal oxides such as LiCoO 2 , LiMn 2 O 4 , and Li(Ni x Mn y Co z )O 2 , vanadium oxides, olivines such as such as LiFePO 4 , sulphur, borates such as LiFeBO 3 , flouro silicates such as LiFeSiO 4 F, lithium, graphite, graphene, lithium-alloying materials, intermetallics, nitrides, oxides, hydrides or silicon.
  • lithium-metal oxides such as LiCoO 2 , LiMn 2 O 4 , and Li(Ni x Mn y Co z )O 2
  • vanadium oxides such as LiFePO 4
  • borates such as LiFeBO 3
  • flouro silicates such as LiFeSiO 4 F
  • lithium, graphite, graphene, lithium-alloying materials intermetallics, n
  • step a) is a DC field.
  • step a) is an AC field.
  • the electric field has a frequency between 1 Hz and 100 MHz.
  • removing the at least some of said solvent is performed by evaporation, heating or a combination thereof.
  • the evaporation may be performed under atmospheric or reduced pressure. Heating may take place during the evaporation.
  • removing the at least some of the said solvent is performed by heating at 50 to 100° C. at atmospheric pressure.
  • removing the at least some of the said solvent is performed by heating at 60 to 80° C. at atmospheric pressure.
  • step a) is between 0.1 and 12.000 cPa ⁇ s.
  • the unit cPa ⁇ s means centiPascal ⁇ second.
  • step a) is between 500 and 1400 cPa ⁇ s.
  • step a) is between 1200 and 500 cPa ⁇ s.
  • the heating may take place at 70° C. at atmospheric pressure during approximately 20 to 25 minutes.
  • the present invention also concerns a battery electrode material comprising a polymer such as a non-cured polymer and conductive particles, wherein said conductive particles are aligned to form at least two lines that are co-linear and/or parallel to each other.
  • a battery electrode material as defined hereinbefore or hereinafter in which the non-cured polymer is a non-curable polymer.
  • a battery electrode material as defined hereinbefore or hereinafter wherein at least one of the at least two lines is straight.
  • a battery electrode material wherein at least one of the at least two lines is dendritic.
  • the battery electrode material as defined hereinbefore or hereinafter and/or produced in accordance with the method as defined hereinbefore or hereinafter may be used in any kind of battery.
  • the battery electrode material produced in accordance with the method as defined hereinbefore or hereinafter may be used in a lithium battery.
  • a battery electrode material as defined hereinbefore or hereinafter wherein the at least one polymer is selected from the group consisting of polyvinyldifluoride (PVDF), carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), poly(3,4-ethylenedioxythiophene) (PEDOT), polyacrylic acid (PAA) and alginate.
  • PVDF polyvinyldifluoride
  • CMC carboxymethylcellulose
  • SBR styrene butadiene rubber
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PAA polyacrylic acid
  • a battery electrode material as defined hereinbefore or hereinafter wherein the conductive particles are electronically or ionically conductive.
  • a battery electrode material as defined hereinbefore or hereinafter wherein the conductive particles have a low aspect ratio.
  • a battery electrode material as defined hereinbefore or hereinafter further comprising active particles.
  • the active particles may be the same or different.
  • the active particles may be randomly distributed in the battery electrode material.
  • the active particles may form lines of active particles or lines of active particles and conductive particles.
  • active particles include, but are not limited to catalyst particles such as platinum, lithium-metal oxides such as LiCoO 2 , LiMn 2 O 4 , and Li(Ni x Mn y Co z )O 2 , vanadium oxides, olivines such as such as LiFePO 4 , sulphur, borates such as LiFeBO 3 , flouro silicates such as LiFeSiO 4 F, lithium, graphite, graphene, lithium-alloying materials, intermetallics, nitrides, oxides, hydrides or silicon.
  • catalyst particles such as platinum, lithium-metal oxides such as LiCoO 2 , LiMn 2 O 4 , and Li(Ni x Mn y Co z )O 2 , vanadium oxides, olivines such as such as LiFePO 4 , sulphur, borates such as LiFeBO 3 , flouro silicates such as LiFeSiO 4 F, lithium,
  • a battery electrode material obtainable according to the method as defined hereinbefore or hereinafter.
  • FIG. 1 shows schematics of the employed alignment procedures for in-plane alignment.
  • FIG. 2 shows schematics of the employed alignment procedures for out-of-plane alignment.
  • FIG. 3 illustrates conductive dendritic structures maximizing the contact area.
  • FIG. 4 shows the life time performance of a LiFePO 4 electrode cycled at an increasing charge/discharge time.
  • the method as defined hereinabove or hereinafter comprises the mixing of infusible conductive particles and a mixture that contains at least one polymer and at least one solvent, and the electric field alignment of conductive particles in this mixture and the control of the viscosity of this mixture by evaporating the solvent.
  • This procedure can be applied to battery electrodes and electrolytes to replace isotropically distributed conductive particles by thin wires of aligned assemblies of conductive particles. These situations are illustrated in FIGS. 1 and 2 .
  • FIG. 1 shows schematics of the employed alignment procedures for in-plane alignment. This displays how randomly distributed conductive particles B mixed with at least one polymer and at least one solvent between electrodes A become arranged into lines of conductive particles B upon application of an electric filed. This figure is for illustrative purposes only, and all of the lines shown may not be formed
  • the solvent may be evaporated in order to obtain a solid material comprising at least one polymer with conductive pathways being lines of conductive particles.
  • the lines of conductive particles extend in a co-linear or substantially parallel fashion with the electrodes and are said to be aligned in an in-plane alignment
  • FIG. 2 shows schematics of the employed alignment procedures for out-of-plane alignment.
  • This displays how randomly distributed conductive particles mixed with at least one polymer and at least one solvent between electrodes A become arranged into lines B upon application of an electric filed.
  • the solvent may be evaporated in order to obtain a solid material comprising at least one polymer with conductive pathways being lines of conductive particles.
  • the electrodes may be provided with holes to allow for evaporation of solvent through the holes.
  • the alignment be also be performed in such a way that at least one of the electrodes is not in direct contact with the conductive particles, the at least one polymer and the at least one solvent.
  • the lines of conductive particles extend in a perpendicular or substantially perpendicular fashion with the electrodes and are said to be aligned in an out-of-plane alignment.
  • the resultant aligned material retains anisotropic properties with respect to directional electrical conductivity. In this way, aligned conductive microstructures of originally infusible particles which do not allow alignment as such are formed.
  • FIG. 3 illustrates dendritic structures maximizing the contact area between conductive lines and the at least one polymer.
  • FIG. 4 shows the life time performance of a LiFePO 4 electrode prepared according to the method of the invention and a LiFePO 4 electrode prepared according to a standard technique cycled at an decreasing charge/discharge time.
  • the electrode prepared according to the method of the invention contains lines of conductive particles whereas the electrode prepared according to a standard technique contains randomly distributed particles. As shown in the figure, the electrode prepared according to the method of the invention retains its capacity to a larger extent than the electrode prepared according to the standard technique.
  • an isotropic material could be manufactured by carrying out the method according to an embodiment of the invention two or more times applying an electric field in different directions.
  • a conducting lattice structure could be formed throughout the material.
  • the method as defined hereinbefore or hereinafter may be used to provide a plurality of conducting lines in a piece of material or to control the conductivity of a piece of material. For instance, the method may be used to create a more highly conducting zone in a piece of material.
  • This example concerns the use of electric field alignment where the alignment is in-plane alignment when preparing polymeric materials in films and membranes with low fraction of electrically conductive particles.
  • This example concerns the preparation of a mixture of conductive particles and polymer matrix that in this example is a polyelectrolyte in solvent; the solvent can be a high alcohol such as propanol.
  • the conductive particles are aligned in the polymer matrix and this alignment enhances the conductivity of material in the alignment direction.
  • This example shows change of the viscosity of the obtained material, by evaporating the solvent, so that the alignment and directional conductivity can be obtained in the alignment step is maintained.
  • the employed conductive particles were carbon nanocones from n-Tec AS or carbon black from Alfa Aesar.
  • the employed polymer was the ionomer Nafion® IQ-1105 (5 wt. % in ethanol).
  • the particles and polymer were mixed such that the particle fraction was 2 vol. % that is at about the percolation threshold of these particles. This mixture was stirred by a magnetic stirrer at room temperature for 15 minutes and visually uniform mixture was obtained.
  • This mixture was spread over the interdigidated gold electrodes on glass substrate.
  • the electrode width was 10 ⁇ m and the electrode spacing 100 ⁇ m.
  • the maximum thickness of the film had a value between 50 and 500 ⁇ m.
  • Alignment was done using 1 kHz field of 0.2 kV/cm.
  • This example is similar to example 1 but instead of using carbon particles at about their percolation threshold, ten times less of material is used.
  • the conductivity increased from ⁇ 10 ⁇ 3 S/m to ⁇ 10 ⁇ 2 S/m.
  • This example is similar to the examples 1 and 2 but instead of in-plane geometry shown in FIG. 1 , the out-of-plane alignment geometry shown in FIG. 2 was used. While the in-plane geometry may provide substrate support to the aligned wires, this is absent in the out-of-plane geometry where wires have translational freedoms perpendicular to the alignment direction. The alignment occurs regardless the geometry, which means that the alignment does not require substrate support.
  • This example is similar to the examples 1-3 but instead of mere carbon particles, carbon particles with platinum catalyst were used. Platinum catalyst does not influence on alignment but the results are identical to those obtained with carbon particles without platinum catalyst.
  • This example concerns partially grown conductive wires in electrodes.
  • particles are grown by an electric field on the current collector surface thus maximizing the available electrode surface area.
  • the growth of aligned wires begins from the electrodes.
  • the alignment was performed using alternating field (1 kV/cm) but particle fraction is kept so low that there are not enough particles to form wires from electrode to electrode. This fraction depends on the particle-polymer pair but is about 0.1 vol. % or less for the 100 ⁇ m electrode spacing.
  • the alignment electrodes become covered by wires that reach the polymer matrix but not the opposite electrode.
  • the obtained “dendritic” electrodes are illustrated in FIG. 3 .

Abstract

The invention concerns a method for manufacturing of a battery electrode material comprising the steps of: a) applying an electric field to at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles will remain in their position when said electric field is removed. Further, the invention concerns a battery electrode material comprising at least one polymer and conductive particles, wherein said conductive particles form at least two lines that are oriented parallel and/or co-linear to each other.

Description

TECHNICAL FIELD
The present invention relates to electrode materials. More specifically, the invention relates to battery electrode materials and to a method for forming such battery electrode materials.
BACKGROUND OF THE INVENTION
Electrochemical devices for energy storage and energy conversion such as batteries and fuel cells contain electrodes and electrolytes to transport and harvest charges. These elements are electrically conductive, ionically conductive or both. These processes may be limited either by the electrode and membrane material's inherent conductivity level or a non-optimal electrode configuration or both.
Rechargeable batteries (or electrochemical cells) contain two electrodes which are connected through an electrolyte. These components may be prepared from a variety of materials but in general the electrode-electrolyte interface often limits efficiency of charge transport. If this interface was larger and if the distance between the electrodes was smaller, the charge transport would be more efficient.
A better electrode design would therefore be influential in improving the battery function.
U.S. Pat. No. 7,828,619 discloses a method for preparing a nanostructured composite electrode through electrophoretic deposition, and electrodes prepared by such a method. A material comprising nanoparticles and carbon nanotubes having a high aspect ratio is directly deposited on the electrode and contains no polymer.
The Journal of Power Sources, 186 (2009), pages 293-298 discloses electric field assisted fabrication of membrane electrode assemblies (MEAs) for fuel cells. Electrodes are produced in which conductive particles are aligned in an ionomer polymer upon application of an electric field. Nothing is mentioned about batteries.
WO 2010/151141 discloses a method for manufacturing an electrostatic discharge device comprising a layer of conductive particles in a cross linked polymer matrix. The method involves curing of the polymer.
In contrast to a fuel cell, which will function as long as fuel and oxygen are supplied to it, a battery will be discharged upon use. Cost and environmental concerns make rechargeable batteries attractive. Other important aspects of batteries are weight and performance after a number of charge/discharge cycles. Batteries having a low weight and/or retaining a high percentage of their initial charge after a large number of charge/discharge cycles are desirable. Common battery electrodes contain carbon and binder in order to improve conductivity. However, the carbon and binder together often constitute approximately 50% of the battery electrode material thereby contributing to the weight of the electrode and eventually the battery. It would be desirable to decrease the battery electrode weight while maintaining and/or improving the battery performance.
SUMMARY OF THE INVENTION
It is an object of the present invention to overcome or at least mitigate some of the disadvantages of the prior art.
Accordingly, in a first embodiment of the invention there is provided a method for manufacturing of a battery electrode material comprising the steps of:
  • a) applying an electric field to at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
  • b) stabilizing the least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles will remain in their position when said electric field is removed.
The present invention is based on the insight that subjecting a mixture comprising at least one polymer and randomly distributed conductive particles to an electric field results in alignment of the conductive particles. In this document, the terms align and alignment are intended to mean that the conductive particles form lines that are oriented in the same or substantially the same direction as the electric field line. It is to be understood that in the context of the lines the term “oriented in the same direction as the electric field line” means that the lines are co-linear or parallel to the electric field line or deviate from the electric field line with an angle of 45° or less. For instance, the direction may be in-plane or out-of-plane as described below. The lines of particles may be co-linear or parallel to each other. The alignment of conductive particles into lines results in conductive pathways in the polymer. Thus, the conductivity will be high in the direction of the lines of conductive particles and low or non-existing in the direction perpendicular to said lines of conductive particles; i.e. the formed battery electrode material will be anisotropic with respect to the direction of conductivity. The pathways are able to enhance the macroscopic conductivity of the material. In particular, the formation of conductive pathways allows the battery electrode material to become conductive also when it contains a lower amount of conductive particles than is otherwise necessary for creating an electrical contact for the material when it contains randomly distributed conductive particles. The amount of conductive particles may thereby be reduced and may be at least ten times lower than the percolation threshold. Concentrations of conductive particles may be in the range of 0.2-10 vol %, 0.2-2 vol %, or 0.2-1.5 vol %. In this document, the percolation threshold is defined as the lowest concentration of conductive particles in the polymer necessary to achieve long range conductivity in a system where the conductive particles are randomly distributed. In this document, long range conductivity refers to the conductivity of the composite comprising conductive particles and at least one polymer. Thus, an advantage associated with the method and battery electrode material of the present invention is that conductivity may be achieved with lower amounts of conductive particles compared to a system using randomly distributed particles. In addition to the reduced amount of conductive particles, this also allows for reducing the amount of binder leading to a battery of less weight and having a higher energy density.
In a further embodiment, there is provided a method as defined hereinbefore or hereinafter wherein the at least one polymer, conductive particles and at least one solvent are mixed prior to being placed between the electrodes in step a).
In a further embodiment, there is provided a method as defined hereinbefore or hereinafter wherein the at least one polymer, conductive particles and at least one solvent are mixed after being placed between the electrodes in step a).
In a further embodiment of the invention, there is provided a method as defined hereinbefore or hereinafter wherein at least one of the at least two lines of conductive particles is straight. In this document, a straight line of particles is defined as a line of particles lacking lines of particles branching out from it.
In still a further embodiment of the invention, there is provided a method as defined hereinbefore or hereinafter wherein at least one of the at least two lines of conductive particles is dendritic. By dendritic is understood that at least one further line of particles branches out from the straight line of particles.
The electric field may be created between electrodes that can be placed either in direct contact with one or both sides of the least one polymer, conductive particles and at least one solvent or outside additional insulating layers. The electrodes may be removed after formation of the battery electrode material.
The direction of the electric field may be determined by the electrode arrangement leading to a specific orientation of the lines of conductive particles.
The lines of conductive particles may extend between the electrodes in an in-plane or out-of-plane direction. When the lines of conductive particles extend in a co-linear or substantially parallel fashion with the electrodes they are said to be aligned in an in-plane alignment. When the lines of conductive particles extend in a perpendicular or substantially perpendicular fashion with the electrodes they are said to be aligned in an out-of-plane alignment.
In a further embodiment of the invention the method as defined hereinbefore or hereinafter further comprises a step comprising supporting said at least one polymer, conductive particles and at least one solvent on a support.
The support may be a glass table, an electrode, a conductive metal foil or an electrode comprising a conductive metal foil. The conductive metal foil may comprise aluminium or copper.
The supporting of the said at least one polymer, conductive particles and at least one solvent on a support includes spreading in order to obtain a layer. The layer may be uniform or non-uniform. The maximum thickness of the layer may be between 5 μm (micrometer) and 2 cm (centimeter). In a further embodiment the maximum thickness of the layer may be between 5 μm and 2 mm (millimetre). In still a further embodiment the maximum thickness of the layer may be between 10 μm and 2 mm.
It will be appreciated that steps a) and b) in the method as defined hereinbefore or hereinafter may at least partly overlap. No or little alignment of the lines of particles will take place if the electric field is in step b) is turned off too early. Step b) may be continued after turning off the electric field in step b) in order to further dry the electrode material after alignment of the lines of conductive particles. The skilled person will understand that the time for drying in step b) will depend on factors such as temperature, pressure, thickness of the layer and the solvent being used. Typically, a layer having a thickness of approximately 50 μm is dried for five minutes between 50 to 100° C., such as 80° C., under atmospheric pressure when the solvent is N-methyl-2-pyrrolidine.
The at least one polymer in the mixture may be a conductive or non-conductive polymer. For instance, the conductive polymer may be an ionomer such as Nafion®. Further, the at least one polymer may be a single kind of polymer or a mixture of different polymers. Suitable polymers include, but are not limited to, polyvinyldifluoride (PVDF), carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), poly(3,4-ethylenedioxythiophene) (PEDOT), polyacrylic acid (PAA) and alginate. The at least one polymer may be curable or non-curable. It will be appreciated that when the at least one polymer is a curable polymer then the removal of the solvent in step b) in the method as defined hereinabove or hereinafter will take place in such a way that no curing takes place.
Thus, in a further embodiment of the invention there is provided a method as defined hereinbefore or hereinafter in which the at least one polymer will not undergo curing when the least one polymer, conductive particles and at least one solvent is stabilized in step b).
Yet, in a further embodiment of the invention there is provided a method as defined hereinbefore or hereinafter wherein the at least one polymer in step a) is a non-curable polymer
The conductive particles are infusible particles such as carbon particles or metal particles. Examples of conductive carbon particles include, but are not limited to, carbon-black, nanocones, carbon nanotubes, graphene particles or disk-like carbon particles. Examples of conductive metal particles include, but are not limited to, silver or iron and oxides thereof. The metallic conductive metal particles may be metallic powders. Further, the conductive particles may be electronically or ionically conductive. The conductive particles may be the same or different.
In a further embodiment of the invention, the conductive particles have a low aspect ratio. However, the invention is not limited to conductive particles having a low aspect ratio. In this document, the aspect ratio is defined as the ratio between the largest linear dimension of a particle such as a conductive particle and the largest dimension perpendicular to said largest dimension. “Low aspect ratio” as used herein refers to an aspect ratio that is equal to or less than 20:1. In a further embodiment of the invention, low aspect ratio refers to an aspect ratio that is equal to or less than 10:1. In a further embodiment of the invention, low aspect ratio refers to an aspect ratio that is equal to or less than 5:1.
In a further embodiment of the invention, the at least one solvent in step a) in the method as defined hereinbefore or hereinafter is water or an organic solvent such as hexane or mixtures thereof. The organic solvent may be miscible or immiscible with water. Further, the organic solvent may be protic or non-protic.
In a further embodiment of the invention, the at least one solvent is N-methyl-2-pyrrolidone (NMP).
In a further embodiment of the invention, there is provided a method according to any previous embodiment, wherein step a) further comprises active particles. The active particles may be the same or different. By active particles is meant particles giving the battery its ability to store lithium ions. Upon application of the electric field in step a) the active particles may align together with the conductive particles. Examples of active particles include, but are not limited to platinum, lithium-metal oxides such as LiCoO2, LiMn2O4, and Li(NixMnyCoz)O2, vanadium oxides, olivines such as such as LiFePO4, sulphur, borates such as LiFeBO3, flouro silicates such as LiFeSiO4F, lithium, graphite, graphene, lithium-alloying materials, intermetallics, nitrides, oxides, hydrides or silicon.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field is of the order of 0.01 to 35 kV/cm.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field is of the order of 0.1 to 10 kV/cm.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field is of the order of 0.1 to 5 kV/cm.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field in step a) is a DC field.
Alternatively, according to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field in step a) is an AC field.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field has a frequency between 1 Hz and 100 MHz.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field has a frequency of 10 Hz.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein the electric field has a frequency of 10 Hz.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein removing the at least some of said solvent is performed by evaporation, heating or a combination thereof. The evaporation may be performed under atmospheric or reduced pressure. Heating may take place during the evaporation.
According to a further embodiment of the invention, there is provided a method according to any embodiment wherein removing the at least some of the said solvent is performed by heating at 50 to 100° C. at atmospheric pressure. In an embodiment of the invention, there is provided a method as defined hereinbefore or hereinafter wherein removing the at least some of the said solvent is performed by heating at 60 to 80° C. at atmospheric pressure. Yet, in an embodiment of the invention there is provided a method as defined hereinbefore or hereinafter in which substantially all of said at least one solvent is removed during step b).
According to a further embodiment of the invention, there is provided a method according to any previous embodiment wherein the viscosity in step a) is between 0.1 and 12.000 cPa·s. The unit cPa·s means centiPascal·second.
According to a further embodiment of the invention, there is provided a method according to any previous embodiment wherein the viscosity in step a) is between 500 and 1400 cPa·s.
According to a further embodiment of the invention, there is provided a method according to any previous embodiment wherein the viscosity in step a) is between 1200 and 500 cPa·s. Further, the heating may take place at 70° C. at atmospheric pressure during approximately 20 to 25 minutes.
The present invention also concerns a battery electrode material comprising a polymer such as a non-cured polymer and conductive particles, wherein said conductive particles are aligned to form at least two lines that are co-linear and/or parallel to each other.
In a further embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter in which the non-cured polymer is a non-curable polymer.
In a further embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter wherein at least one of the at least two lines is straight. Alternatively, there is provided a battery electrode material wherein at least one of the at least two lines is dendritic.
It will be appreciated that the battery electrode material as defined hereinbefore or hereinafter and/or produced in accordance with the method as defined hereinbefore or hereinafter may be used in any kind of battery. In a further embodiment of the invention the battery electrode material produced in accordance with the method as defined hereinbefore or hereinafter may be used in a lithium battery.
According to another embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter wherein the at least one polymer is selected from the group consisting of polyvinyldifluoride (PVDF), carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), poly(3,4-ethylenedioxythiophene) (PEDOT), polyacrylic acid (PAA) and alginate.
According to another embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter wherein the conductive particles are electronically or ionically conductive.
According to another embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter wherein the conductive particles have a low aspect ratio.
According to another embodiment of the invention, there is provided a battery electrode material as defined hereinbefore or hereinafter further comprising active particles. The active particles may be the same or different. The active particles may be randomly distributed in the battery electrode material. Alternatively, the active particles may form lines of active particles or lines of active particles and conductive particles. Examples of active particles include, but are not limited to catalyst particles such as platinum, lithium-metal oxides such as LiCoO2, LiMn2O4, and Li(NixMnyCoz)O2, vanadium oxides, olivines such as such as LiFePO4, sulphur, borates such as LiFeBO3, flouro silicates such as LiFeSiO4F, lithium, graphite, graphene, lithium-alloying materials, intermetallics, nitrides, oxides, hydrides or silicon.
In a further embodiment of the invention, there is provided the use of a battery electrode material as defined hereinbefore or hereinafter in a lithium battery.
In a further embodiment of the invention, there is provided a battery electrode material obtainable according to the method as defined hereinbefore or hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows schematics of the employed alignment procedures for in-plane alignment.
FIG. 2 shows schematics of the employed alignment procedures for out-of-plane alignment.
FIG. 3 illustrates conductive dendritic structures maximizing the contact area.
FIG. 4 shows the life time performance of a LiFePO4 electrode cycled at an increasing charge/discharge time.
 DETAILED DESCRIPTION
In one embodiment of the invention, the method as defined hereinabove or hereinafter comprises the mixing of infusible conductive particles and a mixture that contains at least one polymer and at least one solvent, and the electric field alignment of conductive particles in this mixture and the control of the viscosity of this mixture by evaporating the solvent. This procedure can be applied to battery electrodes and electrolytes to replace isotropically distributed conductive particles by thin wires of aligned assemblies of conductive particles. These situations are illustrated in FIGS. 1 and 2.
FIG. 1 shows schematics of the employed alignment procedures for in-plane alignment. This displays how randomly distributed conductive particles B mixed with at least one polymer and at least one solvent between electrodes A become arranged into lines of conductive particles B upon application of an electric filed. This figure is for illustrative purposes only, and all of the lines shown may not be formed The solvent may be evaporated in order to obtain a solid material comprising at least one polymer with conductive pathways being lines of conductive particles. The lines of conductive particles extend in a co-linear or substantially parallel fashion with the electrodes and are said to be aligned in an in-plane alignment
FIG. 2 shows schematics of the employed alignment procedures for out-of-plane alignment. This displays how randomly distributed conductive particles mixed with at least one polymer and at least one solvent between electrodes A become arranged into lines B upon application of an electric filed. The solvent may be evaporated in order to obtain a solid material comprising at least one polymer with conductive pathways being lines of conductive particles. The electrodes may be provided with holes to allow for evaporation of solvent through the holes. The alignment be also be performed in such a way that at least one of the electrodes is not in direct contact with the conductive particles, the at least one polymer and the at least one solvent. The lines of conductive particles extend in a perpendicular or substantially perpendicular fashion with the electrodes and are said to be aligned in an out-of-plane alignment.
The resultant aligned material retains anisotropic properties with respect to directional electrical conductivity. In this way, aligned conductive microstructures of originally infusible particles which do not allow alignment as such are formed.
FIG. 3 illustrates dendritic structures maximizing the contact area between conductive lines and the at least one polymer.
FIG. 4 shows the life time performance of a LiFePO4 electrode prepared according to the method of the invention and a LiFePO4 electrode prepared according to a standard technique cycled at an decreasing charge/discharge time. The electrode prepared according to the method of the invention contains lines of conductive particles whereas the electrode prepared according to a standard technique contains randomly distributed particles. As shown in the figure, the electrode prepared according to the method of the invention retains its capacity to a larger extent than the electrode prepared according to the standard technique.
Further modifications of the invention within the scope of the claims would be apparent to a skilled person. For example, an isotropic material could be manufactured by carrying out the method according to an embodiment of the invention two or more times applying an electric field in different directions. For example, a conducting lattice structure could be formed throughout the material. Further, the method as defined hereinbefore or hereinafter may be used to provide a plurality of conducting lines in a piece of material or to control the conductivity of a piece of material. For instance, the method may be used to create a more highly conducting zone in a piece of material.
The invention is illustrated, but not limited, by the following Examples.
EXAMPLES Example 1
This example concerns the use of electric field alignment where the alignment is in-plane alignment when preparing polymeric materials in films and membranes with low fraction of electrically conductive particles.
This example concerns the preparation of a mixture of conductive particles and polymer matrix that in this example is a polyelectrolyte in solvent; the solvent can be a high alcohol such as propanol.
The conductive particles are aligned in the polymer matrix and this alignment enhances the conductivity of material in the alignment direction.
This example, moreover, shows change of the viscosity of the obtained material, by evaporating the solvent, so that the alignment and directional conductivity can be obtained in the alignment step is maintained.
The employed conductive particles were carbon nanocones from n-Tec AS or carbon black from Alfa Aesar.
The employed polymer was the ionomer Nafion® IQ-1105 (5 wt. % in ethanol).
The particles and polymer were mixed such that the particle fraction was 2 vol. % that is at about the percolation threshold of these particles. This mixture was stirred by a magnetic stirrer at room temperature for 15 minutes and visually uniform mixture was obtained.
This mixture was spread over the interdigidated gold electrodes on glass substrate. The electrode width was 10 μm and the electrode spacing 100 μm. The maximum thickness of the film had a value between 50 and 500 μm.
Alignment was done using 1 kHz field of 0.2 kV/cm.
The system was stabilized by letting the solvent evaporate during the alignment. This means that the electric field was kept on until the solvent was completely evaporated. At about 25° C., this took 3 minutes for a 100 μm thick film.
Example 2
This example is similar to example 1 but instead of using carbon particles at about their percolation threshold, ten times less of material is used. The conductivity increased from ˜10−3 S/m to ˜10−2 S/m.
Example 3
This example is similar to the examples 1 and 2 but instead of in-plane geometry shown in FIG. 1, the out-of-plane alignment geometry shown in FIG. 2 was used. While the in-plane geometry may provide substrate support to the aligned wires, this is absent in the out-of-plane geometry where wires have translational freedoms perpendicular to the alignment direction. The alignment occurs regardless the geometry, which means that the alignment does not require substrate support.
Example 4
This example is similar to the examples 1-3 but instead of mere carbon particles, carbon particles with platinum catalyst were used. Platinum catalyst does not influence on alignment but the results are identical to those obtained with carbon particles without platinum catalyst.
Example 5
This example concerns partially grown conductive wires in electrodes. In this example particles are grown by an electric field on the current collector surface thus maximizing the available electrode surface area.
The growth of aligned wires begins from the electrodes. In this case the alignment was performed using alternating field (1 kV/cm) but particle fraction is kept so low that there are not enough particles to form wires from electrode to electrode. This fraction depends on the particle-polymer pair but is about 0.1 vol. % or less for the 100 μm electrode spacing. In this case, the alignment electrodes become covered by wires that reach the polymer matrix but not the opposite electrode.
These branched wires become an inherent part of alignment electrodes whose surface area is thus substantially increased.
The obtained “dendritic” electrodes are illustrated in FIG. 3.

Claims (25)

The invention claimed is:
1. A method for manufacturing a battery electrode material, comprising
a) applying an electric field to a mixture comprising at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles remain in their position when said electric field is removed,
wherein the at least one polymer is selected from the group consisting of polyvinyldifluoride, carboxymethylcellulose, styrene butadiene rubber, poly(3,4-ethylenedioxythiophene), polyacrylic acid and alginate.
2. The method according to claim 1, further comprising supporting said mixture comprising at least one polymer, conductive particles and at least one solvent on a support.
3. The method according to claim 1, wherein the at least one polymer is a non-cured polymer.
4. The method according to claim 1, wherein the conductive particles are electronically or ionically conductive.
5. The method according to claim 1, wherein in step a) the mixture further comprises active particles.
6. A method for manufacturing a battery electrode material, comprising
a) applying an electric field to a mixture comprising at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles remain in their position when said electric field is removed,
wherein the conductive particles have a low aspect ratio.
7. The method according to claim 6, further comprising supporting said mixture comprising at least one polymer, conductive particles and at least one solvent on a support.
8. The method according to claim 6, wherein the at least one polymer is a non-cured polymer.
9. The method according to claim 6, wherein the conductive particles are electronically or ionically conductive.
10. The method according to claim 6, wherein in step a) the mixture further comprises active particles.
11. A method for manufacturing a battery electrode material, comprising
a) applying an electric field to a mixture comprising at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles remain in their position when said electric field is removed,
wherein the at least one solvent is N-methyl-2-pyrrolidone.
12. The method according to claim 11, further comprising supporting said mixture comprising at one least polymer, conductive particles and at least one solvent on a support.
13. The method according to claim 11, wherein the at least one polymer is a non-cured polymer.
14. The method according to claim 11, wherein the conductive particles are electronically or ionically conductive.
15. The method according to claim 11, wherein in step a) the mixture further comprises active particles.
16. A method for manufacturing a battery electrode material, comprising
a) applying an electric field to a mixture comprising at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles remain in their position when said electric field is removed,
wherein the viscosity of the mixture in step a) is between 0.1 and 12,000 cPa·s.
17. The method according to claim 16, further comprising supporting said mixture comprising at least one polymer, conductive particles and at least one solvent on a support.
18. The method according to claim 16, wherein the at least one polymer is a non-cured polymer.
19. The method according to claim 16, wherein the conductive particles are electronically or ionically conductive.
20. The method according to claim 16, wherein in step a) the mixture further comprises active particles.
21. A method for manufacturing a battery electrode material, comprising
a) applying an electric field to a. mixture comprising at least one polymer, conductive particles and at least one solvent whereby said conductive particles become arranged between the electrodes in at least two lines that are oriented in the same direction as the electric field line, and
b) stabilizing the at least one polymer, conductive particles and at least one solvent by removing at least some of said at least one solvent while maintaining the electric field in step a) whereby the at least two lines of conductive particles remain in their position when said electric field is removed,
wherein the electric field is of the order of 0.1 to 10 kV/cm.
22. The method according to claim 21, further comprising supporting said mixture comprising at least one polymer, conductive particles and at least one solvent on a support.
23. The method according to claim 21, wherein the at least one polymer is a non-cured polymer.
24. The method according to claim 21, wherein the conductive particles are electronically or ionically conductive.
25. The method according to claim 21, wherein in step a) the mixture further comprises active particles.
US13/996,781 2010-12-21 2011-12-21 Battery electrode material and method for making the same Active 2034-01-09 US9780354B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO20101791 2010-12-21
NO20101791 2010-12-21
PCT/EP2011/073621 WO2012085105A1 (en) 2010-12-21 2011-12-21 Battery electrode material and method for making the same

Publications (2)

Publication Number Publication Date
US20130316245A1 US20130316245A1 (en) 2013-11-28
US9780354B2 true US9780354B2 (en) 2017-10-03

Family

ID=45418687

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/996,781 Active 2034-01-09 US9780354B2 (en) 2010-12-21 2011-12-21 Battery electrode material and method for making the same

Country Status (2)

Country Link
US (1) US9780354B2 (en)
WO (1) WO2012085105A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9169601B2 (en) * 2010-12-15 2015-10-27 Condalign As Method for forming an anisotropic conductive paper and a paper thus formed
US9818499B2 (en) 2011-10-13 2017-11-14 Flexcon Company, Inc. Electrically conductive materials formed by electrophoresis
US8673184B2 (en) 2011-10-13 2014-03-18 Flexcon Company, Inc. Systems and methods for providing overcharge protection in capacitive coupled biomedical electrodes
US9882198B2 (en) * 2014-02-04 2018-01-30 The Regents Of The University Of Michigan High performance lithium battery electrodes by self-assembly processing
EP3109928B1 (en) * 2015-06-24 2019-08-14 Airbus Defence and Space GmbH Method for producing an electrode, in particular for electrochemical energy storage and electrode and electrochemical energy storage
US10804524B2 (en) * 2017-11-14 2020-10-13 The Curators Of The University Of Missouri Controlling structures of battery electrodes
CN111477892B (en) * 2020-05-27 2021-09-28 广西师范大学 V, N co-doped graphene Pt-supported catalyst and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5777292A (en) * 1996-02-01 1998-07-07 Room Temperature Superconductors Inc. Materials having high electrical conductivity at room teperatures and methods for making same
WO2006057704A2 (en) 2004-11-24 2006-06-01 The Arizona Board Of Regents, A Body Corporate Acting On Behalf Of Arizona State University Electrorheological design and manufacturing method for proton transport membranes and bipolar plates
US20070062029A1 (en) * 2005-08-26 2007-03-22 Sanyo Electric Co., Ltd. Method of producing electrode plate filled with active material, method of producing battery using thereof
US20090038832A1 (en) 2007-08-10 2009-02-12 Sterling Chaffins Device and method of forming electrical path with carbon nanotubes
US7828619B1 (en) * 2005-08-05 2010-11-09 Mytitek, Inc. Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby
US20120231178A1 (en) 2009-06-22 2012-09-13 Condalign As Anisotropic conducting body and method of manufacture

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5777292A (en) * 1996-02-01 1998-07-07 Room Temperature Superconductors Inc. Materials having high electrical conductivity at room teperatures and methods for making same
WO2006057704A2 (en) 2004-11-24 2006-06-01 The Arizona Board Of Regents, A Body Corporate Acting On Behalf Of Arizona State University Electrorheological design and manufacturing method for proton transport membranes and bipolar plates
US7828619B1 (en) * 2005-08-05 2010-11-09 Mytitek, Inc. Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby
US20070062029A1 (en) * 2005-08-26 2007-03-22 Sanyo Electric Co., Ltd. Method of producing electrode plate filled with active material, method of producing battery using thereof
US20090038832A1 (en) 2007-08-10 2009-02-12 Sterling Chaffins Device and method of forming electrical path with carbon nanotubes
US20120231178A1 (en) 2009-06-22 2012-09-13 Condalign As Anisotropic conducting body and method of manufacture

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
International Search Report issued Apr. 5, 2012 in PCT/EP2011/073621.
Search Report issued Jul. 21, 2011 in Norwegian Patent Application No. 20101791.
U.S. Appl. No. 13/380,189, filed May 25, 2012, Svasand, et al.
WANG, Z.T. ; WANG, Y.X. ; XU, L. ; GAO, Q.J. ; WEI, G.Q. ; LU, J.: "Electric field-treated MEAs for improved fuel cell performance", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 186, no. 2, 15 January 2009 (2009-01-15), CH, pages 293 - 298, XP025839930, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2008.10.065
Zhi-Tao Wang, et al., "Electric field-treated MEAs for improved fuel cell performance", Journal of Power Sources, vol. 186, No. 2, Jan. 15, 2009, XP025839930, pp. 293-298.

Also Published As

Publication number Publication date
US20130316245A1 (en) 2013-11-28
WO2012085105A1 (en) 2012-06-28

Similar Documents

Publication Publication Date Title
US9780354B2 (en) Battery electrode material and method for making the same
Wang et al. Lithium-salt-rich PEO/Li0. 3La0. 557TiO3 interpenetrating composite electrolyte with three-dimensional ceramic nano-backbone for all-solid-state lithium-ion batteries
Chen et al. Configurational and structural design of separators toward shuttling-free and dendrite-free lithium-sulfur batteries: A review
KR101774683B1 (en) Electorde active material slurry, preparation method thereof, and all solid secondary battery comprising the same
Park et al. Effect of polymeric binder type on the thermal stability and tolerance to roll-pressing of spherical natural graphite anodes for Li-ion batteries
Zheng et al. Cooperation between active material, polymeric binder and conductive carbon additive in lithium ion battery cathode
CN109786817B (en) Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane
KR20120025518A (en) Batteries utilizing anode coating directly on nanoporous separators
CN102549691A (en) Current collectors having textured coating
CN105098234A (en) Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material
Sun et al. Effect of poly (acrylic acid)/poly (vinyl alcohol) blending binder on electrochemical performance for lithium iron phosphate cathodes
JP6916815B2 (en) Electrodes for secondary batteries, secondary batteries, and their manufacturing methods
Kim et al. Uniform metal-ion flux through interface-modified membrane for highly stable metal batteries
Wei et al. Achieving a high loading Si anode via employing a triblock copolymer elastomer binder, metal nanowires and a laminated conductive structure
Fan et al. Facile fabrication of polyether sulfone (PES) protecting layer on Cu foil for stable Li metal anode
CN105322145A (en) Lithium ferric manganese phosphate/graphene/ carbon composite material and preparation method and application
Huang et al. Design of conductive binders for LiFePO4 cathodes with long-term cycle life
Karuppiah et al. Patterning and a composite protective layer provide modified li metal anodes for dendrite-free high-voltage solid-state lithium batteries
CN109148840B (en) PEO-PVA-based binder for lithium-sulfur batteries
Yuan et al. Baseline Si electrode fabrication and performance for the battery for Advanced Transportation Technologies Program
KR20150042350A (en) Manufacturing method of carbon fiber sheet current collector for all solid state rechargeable thin film lithium secondary battery, and all solid state rechargeable thin film lithium secondary battery comprising carbon fiber sheet current collector
KR20130140551A (en) 3-d complex electrode having multi-active material and flexible lithium rechargeable batteries comprising the same
JP5515257B2 (en) Bipolar secondary battery
Yan et al. Sandwich-structured cathodes with cross-stacked carbon nanotube films as conductive layers for high-performance lithium-ion batteries
KR20130049441A (en) Composition of electrode active agent, method for preparing the same, and electrochemical capacitor using the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: CONDALIGN AS, NORWAY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BUCHANAN, MARK;HELGESEN, GEIR;KNAAPILA, MATTI;AND OTHERS;SIGNING DATES FROM 20130531 TO 20130619;REEL/FRAME:030688/0209

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

FEPP Fee payment procedure

Free format text: SURCHARGE FOR LATE PAYMENT, SMALL ENTITY (ORIGINAL EVENT CODE: M2554); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2551); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Year of fee payment: 4